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At least 361 records · Page 20

Cool outflows in MaNGA: a systematic study and comparison to the warm phase

ABSTRACT This paper investigates the neutral gas phase of galactic winds via the Na i Dλλ5890, 5895Å feature within z ∼ 0.04 MaNGA galaxies and directly compares their incidence and strength to the ionized winds detected within the same parent sample. We find evidence for neutral outflows in 127 galaxies (∼5 per cent of the analysed line-emitting sample). ${\rm Na\, \small {\rm I}\ D}$ winds are preferentially seen in galaxies with dustier central regions and both wind phases are more often found in systems with elevated star formation rate (SFR) surface densities, especially when there has been a recent upturn in the star formation activity according to the $\rm SFR_{5 \, Myr}/SFR_{800 \, Myr}$ parameter. We find the ionized outflow kinematics to be in line with what we measure in the neutral phase. This demonstrates that, despite their small contributions to the total outflow mass budget, there is value to collecting empirical measurements of the ionized wind phase to provide information on bulk motion in the outflow. Depending on dust corrections applied to the ionized gas diagnostics, the neutral phase has ∼1.2−1.8 dex higher mass outflow rates ($\dot{M}_{\rm out}$), on average, compared to the ionized phase. We quantify scaling relations between $\dot{M}_{\rm out}$ and the strengths of the physical wind drivers (SFR, LAGN). Using a radial–azimuthal stacking method, and by considering inclination dependencies, we find results consistent with biconical outflows orthogonal to the disc plane. Our work complements other multiphase outflow studies in the literature that consider smaller samples, more extreme objects, or proceed via stacking of larger samples.

79 ASTRONOMY AND ASTROPHYSICS↗

Quantification of trace iodine using laser-induced breakdown spectroscopy for real-time monitoring of nuclear off-gas streams

This study evaluated the potential of laser-induced breakdown spectroscopy (LIBS) for real-time monitoring of trace gas-phase iodine, which is an element of high significance in nuclear applications due to its long radioactive half-life (as iodine-129), volatility, and biological impact. In anticipation of iodine evolving into off-gas systems in molten salt reactor and nuclear fuel recycling applications, this research aimed to assess LIBS performance in flowing argon and helium matrices; optimize measurement parameters using a multichannel spectrometer; and perform calibrations to assess predictive capabilities and limits of detection (LODs). Experimental results successfully measured gas-phase iodine in flowing argon and helium; however, trace iodine was not detected in air. Optimal delay times were determined to be 10 µs for argon and 1 µs for helium, which are consistent with the expected shorter plasma lifetime in helium relative to argon. An emission line survey was provided with the 206.16, 804.37, 902.24, and 905.83 nm peaks, which were identified as the strongest emission peaks. Calibration models were successfully built in both helium and argon, achieving LODs down to 3 ppm in helium and 5 ppm in argon. The iodine emission at 905.83 nm emerged as the most robust for calibration and was subsequently applied to a time series dataset in argon. The predictive trace confirmed the feasibility of employing LIBS for continuous, online quantification of trace iodine in flowing gas systems.

Andrews, Hunter B. [Oak Ridge National Laboratory ↗

High Free-Tropospheric Aitken-Mode Aerosol Concentrations Buffer Cloud Droplet Concentrations in Large-Eddy Simulations of Precipitating Stratocumulus

A new Aitken mode aerosol microphysics scheme is developed for a large eddy simulation model in order to better investigate cloud-aerosol interactions in the marine boundary layer and to study the Aitken buffering hypothesis of McCoy et al. (2021), https://doi.org/10.1029/2020jd033529. This scheme extends the single-mode two-moment prognostic aerosol scheme of Berner et al. (2013), https://doi.org/10.5194/acp-13-12549-2013. Seven prognostic variables represent accumulation and Aitken log-normal aerosol modes in air and droplets as well as 3 gas species. Scavenging of interstitial and other unactivated aerosol by cloud and rain drops are treated using the scheme described in Berner et al. (2013), https://doi.org/10.5194/acp-13-12549-2013. The scheme includes coagulation of unactivated aerosol and a simple chemistry model with gas phase H 2 SO 4 , SO 2 , and DMS as prognostic variables to capture basic influences of sulfur chemistry on the model aerosols. Nucleation of H 2 SO 4 aerosol particles from gas-phase H 2 SO 4 is neglected. A deep, precipitating stratocumulus case (VAMOS Ocean Cloud Atmosphere Land Study RF06) is used to test the new scheme. The presence of the Aitken mode aerosol increases the cloud droplet concentration through activation of the larger Aitken particles and delays the creation of an ultraclean, strongly precipitating cumulus state. Scavenging of unactivated accumulation and Aitken particles by cloud and precipitation droplets accelerates the collapse. Increasing either the above-inversion Aitken concentration or the surface Aitken flux increases the Aitken population in the boundary layer and prevents the transition to an ultraclean state.

54 ENVIRONMENTAL SCIENCES↗

Predictive Chemical Kinetic Modeling: Where We Succeed, Where We Struggle, and What Comes Next

Chemical kinetic modeling plays a foundational role in fields ranging from energy to environmental science, pharmaceuticals, and advanced materials. The past two decades have seen remarkable progress, particularly in modeling gas-phase reactions for thermochemical processes, leading to impactful industrial applications such as steam cracking and air quality management. However, new challenges are emerging. The successful development of systematic methodologies for the description of gas-phase kinetics opens the possibility to apply the same approach to the study of more challenging systems. Here, we review recent advances, including ab initio transition state theory-based master equation estimation of elementary rates, automated mechanism generation, machine-learning-assisted kinetics, and uncertainty quantification, and discuss the advances needed to apply the same methodological approach in areas such as heterogeneous catalysis, electrochemistry, liquid-phase and solid-state reactivity, and multiscale model integration. We advocate for the development of targeted tools, especially methods that go beyond empirical tuning toward first-principles-based predictions. We highlight the need for accessible software and AIaugmented workflows to democratize modeling for industry and academia alike. In this perspective, we call attention to not only what has worked but also what remains unsolved, advocating to avoid overemphasizing successes in scientific works at the expense of realism. The next decade should focus on predictive capability, physical accuracy, and community infrastructure (e.g., databases and services) to enable innovation across diverse fields. We argue that kinetic modeling, properly equipped, can accelerate discovery far beyond its traditional domains.

ab initio calculations↗

Photoinduced hydrogen dissociation in thymine predicted by coupled cluster theory

The fate of thymine upon excitation by ultraviolet radiation has been the subject of intense debate. Today, it is widely believed that its ultrafast excited state gas phase decay stems from a radiationless transition from the bright ππ* state to a dark nπ* state. However, conflicting theoretical predictions have made the experimental data difficult to interpret. Here we simulate the early gas phase ultrafast dynamics in thymine at the highest level of theory to date. This is made possible by performing wavepacket dynamics with a recently developed coupled cluster method. Our simulation confirms an ultrafast ππ* to nπ* transition (τ = 41 ± 14 fs). Furthermore, the predicted oxygen-edge X-ray absorption spectra agree quantitatively with experiment. We also predict an as-yet uncharacterized πσ* channel that leads to hydrogen dissociation at one of the two N-H bonds. Similar behavior has been identified in other heteroaromatic compounds, including adenine, and several authors have speculated that a similar pathway may exist in thymine. However, this was never confirmed theoretically or experimentally. This prediction calls for renewed efforts to experimentally identify or exclude the presence of this channel.

Kjønstad, Eirik F.↗

Mechanistic Insights for Plasma-Catalytic CO 2 Reduction over TiO 2 in a Dielectric Barrier Discharge Reactor

Reaction kinetics experiments coupled with phenomenological kinetic modeling and parameter estimation are used to elicit insights into the mechanism and active sites for the plasma-catalytic dissociation of CO 2 on TiO 2 . Experimental and model insights showed that gas-phase reactions contribute at least two-thirds of the overall product formation at explored conditions; weak temperature dependence, strong sensitivity to specific energy input (SEI), apparent first order in CO 2 , and positive influence of cofed argon (Ar) and oxygen (O 2 ) for the gas-phase contributions all suggest that expected plasma reaction steps such as electron-impact and high-energy collisions are the dominant modes for CO 2 dissociation. The Arrhenius-like expression for gas contributions resulted in a preexponential of 4.40 × 10 –3 s –1 , an E SEI,g of 7.90 × 10 –4 mol/kJ, and an E a,g of 1.00 × 10 –3 J/mol. For surface contributions, the small apparent barrier of 16.3 kJ/mol, relatively weaker dependence on SEI, first-order dependence on CO 2 , and insensitivity to cofed Ar and O 2 all point to CO 2 dissociation on TiO 2 surface facets without vacancies and aided by plasma (leading to vibrationally excited CO 2 and/or a reactive surface with significant surface charge accumulation). The Arrhenius-like expression resulted in a preexponential of 7.81 × 10 –2 s –1 , an E SEI,s of 1.90 × 10 –3 mol/kJ, and an E a,s of 1.63 × 10 4 J/mol. The derived kinetic model further enabled a systematic evaluation of the effect of inputs (plasma power, flow rate, CO 2 inlet concentration, and temperature) to identify process trends and optimal operating conditions.

catalyst↗

Modeling of the spray-induced wall stress acting on the ignition assistance device

This research introduces a novel wall-stress model called the Spray-Induced Wall Stress (SIWS) model, which considers the effects of spray-wall impingement and the resulting formation of wall stress within the Lagrangian spray modeling framework. The primary objective of this paper is to provide a mathematical description of the fundamental physics underlying the model. Subsequently, the proposed model is validated using existing experimental data. Here, the remainder of the study focuses on the practical application of the model to an ignition assistance device. Specifically, this device is installed in a compression ignition engine and designed to enhance ignition in aviation-fueled high-altitude aircraft propulsion systems. The research sheds light on the mechanical impulse caused by the high-speed impact of the spray jet, leading to the accumulation of mechanical stress on the rigid body of the ignition assistance device. Previous studies on fluid-structure interaction have only considered the interaction between the gas phase and the solid wall. However, the SIWS model incorporates the additional impact of the impinging liquid spray jet. Consequently, the simulated stress distribution on the ignition assistance device can be estimated by considering both the gas-phase-induced term and the spray-induced term simultaneously.

33 ADVANCED PROPULSION SYSTEMS↗

Mechanism of the Non‐Kasha Fluorescence in Pyrene

The high-energy shoulder in the gas-phase fluorescence emission spectrum of pyrene is a well-known example of non-Kasha emission. Here, we comparatively assess two approaches, vibronic perturbation theory and nonadiabatic dynamics, in their ability to predict and explain the gas-phase fluorescence spectrum of pyrene. While both methods qualitatively capture the non-Kasha emission, they differ in their computational requirements, accuracy, and physical interpretation. Vibronic perturbation theory and nonadiabatic dynamics are complementary and can be combined in a two-step approach to non-Kasha fluorescence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electric field dynamics in an atmospheric pressure helium plasma jet impinging on a substrate

Time and spatially resolved electric field measurements by Stark polarization spectroscopy in a nanosecond pulsed atmospheric pressure helium jet operating in ambient air and impinging on a conductive indium tin oxide (ITO) coated glass slide are reported. An automatic fitting procedure of the Stark shifted spectra taking into consideration constraints regarding Stark components positions and intensities as well as molecular nitrogen emission subtraction was implemented. This allowed electric field vector components measurements both in the gas phase and at the interface when the jet impinges on the substrate and during the development of a surface ionization wave. The obtained results show an increase of the axial electric field in the jet effluent in the gas phase with a peak magnitude from 12 to 18 kVcm -1 before the ionization wave impinges on the substrate. A steep electric field enhancement to a peak value of about 24 kVcm -1 was observed when the ionization wave impinges on the surface. A peak radial electric field of about 27 kVcm -1 was measured off-axis in the surface ionization wave. These results are consistent with previously reported modelling predictions. While Stark polarization spectroscopy is limited to electric field measurement from regions with emission, we illustrate that the capability to measure near surface electric fields in helium makes it a valuable complementary technique for the electric field-induced second harmonic (E-FISH) technique.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Resonance-stabilized radical clustering bridges the gap between gaseous precursors and soot in the inception stage

Carbonaceous particles are widespread in combustion, atmospheric, extraterrestrial, and nanomaterials environments. Resonance-stabilized radicals (RSRs) are commonly identified in fuel combustion and pyrolysis processes and play an essential role in carbonaceous particle formation. Despite their importance, comprehensive experimental and mechanistic understanding of particle inception through RSR reactions is lacking. This work investigated particle size distribution, chemical composition, and thermal behavior of soot particles generated by the flow reactor pyrolysis reactions of typical RSRs, in particular, 1-indenyl, 1-methylnaphthyl, and 2-methylnaphthyl radicals, and by the pyrolysis of hydrocarbons with a variety of structures. Particle size distributions show soot particles with mobility diameters in an incipient-particle range of 1.3 to 1.6 nm. Laser desorption/ionization mass spectrometry results suggest that soot products consist of much larger covalently bound clusters (CBCs) than those observed in the gas phase. Under our experimental conditions, the CBCs exhibit a phase transition for particles with calculated molecular diameters of around 1.5 nm. Evaporation experiments and thermogravimetric analysis of the soot products reveal distinct thermal characteristics for small and large CBCs. These results implicate CBCs as bridges between gas-phase species and soot particles. The present work provides a soot-inception mechanism called RSR clustering (RSRC) that is characterized by the reactive clustering of RSRs. The RSRC mechanism contrasts with conventional soot formation models that attribute soot inception primarily to the aggregation of large-size polycyclic aromatic hydrocarbons.

carbonaceous particle↗

Removal of trace gases can both increase and decrease cloud droplet formation

Aerosols consist of liquid or solid particles dispersed in a gas. Aerosol measurements generally rely on drying the particles before quantifying their physicochemical properties. This drying can potentially remove semivolatile compounds from the particles. Here, we show size-resolved cloud condensation nuclei (CCN) measurements quantifying the hygroscopicity parameter in the presence and absence of a denuder. The denuder efficiently removed alkanes and weakly functionalized acids, aldehydes, and alcohols with fewer than 10 carbon atoms from the gas phase. Denuding organic compounds perturbed the CCN-derived hygroscopicity parameter by up to 50%. Denuding either rendered the particles more or less CCN active, and the direction of the effect depended on sample relative humidity and trace gas concentration. The effect was weakest in early spring and strongest in late spring and summer. The measurements demonstrate an unexpectedly strong coupling between the particle and gas phase, influencing CCN activity through either volatilization or surface adsorption, or both.

54 ENVIRONMENTAL SCIENCES↗

Where Is the Water? Jupiter-like C/H Ratio but Strong H{sub 2}O Depletion Found on τ Boötis b Using SPIRou

The present-day envelope of gaseous planets is a relic of how these giant planets originated and evolved. Measuring their elemental composition therefore presents a powerful opportunity to answer long-standing questions regarding planet formation. Obtaining precise observational constraints on the elemental inventory of giant exoplanets has, however, remained challenging owing to the limited simultaneous wavelength coverage of current space-based instruments. Here, we present thermal emission observations of the nontransiting hot Jupiter τ Boo b using the new wide wavelength coverage (0.95–2.50 μm) and high spectral resolution (R = 70,000) CFHT/SPIRou spectrograph. By combining a total of 20 hr of SPIRou data obtained over five nights in a full atmospheric retrieval framework designed for high-resolution data, we constrain the abundances of all the major oxygen- and carbon-bearing molecules and recover a noninverted temperature structure using a new free-shape, nonparametric temperature–pressure profile retrieval approach. We find a volume mixing ratio of log(CO) = -2.46{sub -0.29}{sup +0.25} and a highly depleted water abundance of less than 0.0072 times the expected value for a solar composition envelope. Combined with upper limits on the abundances of CH{sub 4}, CO{sub 2}, HCN, TiO, and C{sub 2}H{sub 2}, this results in a gas-phase C/H ratio of 5.85{sub -2.82}{sup +4.44} × solar, consistent with the value of Jupiter, and an envelope C/O ratio robustly greater than 0.60, even when taking into account the oxygen that may be sequestered out of the gas phase. Combined, the inferred supersolar C/H, O/H, and C/O ratios on τ Boo b support a formation scenario beyond the water snowline in a disk enriched in CO owing to pebble drift.

74 ATOMIC AND MOLECULAR PHYSICS↗

Data–driven and constrained optimization of semi–local exchange and nonlocal correlation functionals for materials and surface chemistry

Reliable predictions of surface chemical reaction energetics require an accurate description of both chemisorption and physisorption. Herein, we present an empirical approach to simultaneously optimize semi-local exchange and nonlocal correlation of a density functional approximation to improve these energetics. A combination of reference data for solid bulk, surface, and gas-phase chemistry and physical exchange-correlation model constraints leads to the VCML-rVV10 exchange-correlation functional. Owing to the variety of training data, the applicability of VCML-rVV10 extends beyond surface chemistry simulations. It provides optimized gas phase reaction energetics and an accurate description of bulk lattice constants and elastic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanistic Understanding of Methane Combustion over Ni/CeO 2 : A Combined Experimental and Theoretical Approach

Catalytic oxidation of methane (CH 4 ) over nonprecious Ni/CeO 2 catalysts has received a lot of attention due to the large natural gas reserves found in North America and the prohibitive cost of palladium-based catalysts, commonly used for CH 4 oxidation. However, the catalytic mechanism of CH 4 oxidation over Ni/CeO 2 still remains unclear. Moreover, the parameters affecting the reaction rates, the interaction between nickel and CeO 2 , and the reaction intermediates are still not well understood. In this study, kinetic model fitting, CH 4 temperature-programmed reduction-mass spectroscopy (CH 4 TPR-MS), in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory (DFT) calculations were combined to elucidate the mechanism of complete oxidation of CH 4 over Ni/CeO 2 . CH 4 TPR-MS showed that the complete oxidation of CH 4 over Ni/CeO 2 requires 55–120 °C lower compared to bare CeO 2 or Ni/quartz sand; complete oxidation of CH 4 took place when the surface oxygen species were abundant, while partial oxidation products (CO, H 2 ) were formed when the oxygen species were depleted. In situ DRIFTS showed that CH 3 , CH 2 , CO, and CO 2 were formed after CH 4 activation over Ni/CeO 2 , while CH 3 O species were not observed. Combining those findings with kinetic model fitting, a redox Mars–van Krevelen (MvK) mechanism showed the best description of the experimental observations. The MvK mechanism involves the reaction of dissociated oxygen species with gas-phase CH 4 while water inhibits the reaction rate by adsorbing on the oxidized sites. Moreover, CH 4 activation leads to the reduction of the active sites and oxygen vacancy formation followed by reoxidation of the active sites by gas-phase O 2 . A CH 4 oxidation reaction pathway over Ni/CeO 2 is proposed by DFT calculations. In summary, the findings shown here suggest that CH 4 oxidation over Ni/CeO 2 follows a redox MvK mechanism and provides guidance for the rational design of non-precious-metal catalysts for CH 4 oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxidation in laser-generated metal plumes

The temporal evolution of atoms and molecules in a laser-produced plasma was investigated using optical emission spectroscopy for several metal targets (i.e., Al, Ti, Fe, Zr, Nb, and Ta). Plasmas from metal targets were generated by focusing 1064 nm, 6 ns pulses from an Nd:YAG laser. Gas-phase oxidation/plasma chemistry was initiated by adding O2 (partial pressures up to ≈20%) to an N2 environment where the total background pressure was kept at a constant 1 atmosphere. Temporally resolved emission spectral features were used to track the gas-phase oxidation. The dynamics of atomic and molecular species were monitored using space-resolved time-of-flight emission spectroscopy. Our results highlight that the partial pressure of O2 strongly influences spectral features and molecular formation in laser-produced plasmas. Atoms and molecules co-exist in plasmas, although with different temporal histories depending on the target material due to differences in thermo- and plasma chemical reactions occurring in the plume.

Kautz, Elizabeth J. (ORCID:0000000263389223)↗

Molecular structure and catalytic promotional effect of Mn on supported Na 2 WO 4 /SiO 2 catalysts for oxidative coupling of methane (OCM) reaction

The structure and promotional effect of Mn in supported Mn-Na 2 WO 4 /SiO 2 catalysts for the oxidative coupling of methane (OCM) reaction has been debated for a longtime in the literature. In the current investigation, with the aid of multiple in-situ characterization studies, we show that the freshly calcined supported 1.2Mn-5Na 2 WO 4 /SiO 2 catalyst possesses crystalline Na 2 WO 4 , Mn 2 O 3 and SiO 2 (cristobalite phase) along with surface MnO x and Na-WO x sites at low temperature and oxidizing environments. Under the OCM reaction environment (T>800°C), the crystalline Na 2 WO 4 phase melts and Mn 2 O 3 phase reduces. In contrast, the surface MnO x and Na-WO x sites exhibit excellent thermal and chemical stability. Exposure of the 1.2Mn-5Na 2 WO 4 /SiO 2 catalyst to the OCM reaction environment redisperses the molten Na 2 WO 4 phase on the SiO 2 support to form new surface WO x sites. Interestingly, the stable MnO x species interacts with both molten Na 2 WO 4 phase and surface Na-WO x sites during OCM reaction. Controlled transient kinetic experiments in TAP and detailed steady state OCM fixed-bed reaction studies reveal the role and promotional effect of Mn in the 1.2Mn-5Na 2 WO 4 /SiO 2 catalyst. The W-oxides (both molten Na 2 WO 4 and surface Na-WO x sites) are the active sites for the catalytic OCM reaction and the MnO x species only function as promoters. The promotion of MnO x strongly depends on the gas phase O 2 partial pressure and the MnO x species act as mediators for oxygen exchange between the gas phase molecular O 2 and catalyst lattice oxygen. In conclusion, the temperature dependent MnO x promotion reveals that the MnO x species selectively promote the molten Na 2 WO 4 phase at lower reaction temperature and the surface Na-WO x sites at higher temperature.

36 MATERIALS SCIENCE↗

Exploring the Coexistence of Spin States in [Fe(tpy-Ph) 2 ] 2+ Complexes on Au(111) Using DFT Calculations

In this work, we systematically study the electronic structure and stability of spin states of the [Fe-(tpy-ph) 2 ] 2+ molecule in both the gas phase and on a Au(111) substrate using density functional theory + U (DFT+ U ) calculations. We find that the stability of the Fe 2+ ion’s spin states predicted by the computations is significantly influenced by the Hubbard U parameter. In the gas phase, the low-spin (LS, S = 0) state is found to be energetically favorable for U (Fe) ≤ 3 eV, whereas the high-spin (HS, S = 2) state is stabilized for U (Fe) > 3 eV. Interaction with the Au(111) substrate is found to elevate the critical U for the spin-state transition to 3.5 eV. Additionally, we perform L-edge X-ray absorption spectroscopy (XAS) calculations for both HS and LS states. The calculated XAS suggests that the HS state more closely aligns with the experimental observations, indicating the potential coexistence of the HS state as the initial state during the X-ray excitation process. These findings enrich our understanding of spin-state dynamics in [Fe(tpy-Ph) 2 ] 2+ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasma ammonia synthesis over mesoporous silica SBA-15

Herein we demonstrate the synthesis of ammonia via atmospheric DBD plasma discharge over silica. We evaluated the performance of three structural different silicas: non-porous silica, fumed-silica and mesoporous SBA-15 silica. The mesoporous SBA-15 sample resulted in an ammonia synthesis rate per gram of catalyst at least 3 times higher than that of the non-porous and fumed silica when employing a hydrogen rich gas feed. The hierarchical ordered pore size in the mesoporous range of SBA-15 allowed us to observe experimentally, the pore size effect in the plasma discharge. Specifically, the ammonia production is enhanced by the presence of mesopores that can effectively enable the discharge diffusion into the pore as predicted by theoretical calculations. The importance of the porous structure was confirmed by optical emission spectra which indicates a similarity on the relative intensity on the main plasma activated species in the gas phase such as N2+, NH and H_α for the three silicas employed in this work i.e., non-porous, fumed and mesoporous (SBA-15). Furthermore, the remarkable ammonia production when employing the SBA-15 shows that despite the similarities in the gas phase the main differences might be attributed to the diffusion of the plasma discharge into the pores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗